Observation of Haldane magnetism in organically templated vanadium phosphate (enH2)0.5VPO4OH.

We prepared an organically templated magnet, (enH2)0.5VPO4OH (enH2 = diprotonated ethylenediamine), hydrothermally and characterized its crystal structure by powder X-ray diffraction and Fourier-transform infrared spectroscopy, and its physical properties by magnetization, specific heat and nuclear magnetic resonance measurements and density functional theory calculations. (enH2)0.5VPO4OH consists of uniform chains of V3+ (d2, S = 1) ions and exhibits Haldane magnetism with spin gap Δ = 59.3 K from the magnetic susceptibility χ(T) at µ0H = 0.1 T, which is reduced to 48.4 K at µ0H = 9 T according to the 31P shift. The NMR data evidence the formation of a spin-glass state of unpaired S = 1/2 spins at TS-G ≈ 3 K and indicate that the Haldane S = 1 spin chain segments are much longer in the organically templated magnet (enH2)0.5VPO4OH than in the ammonium counterpart NH4VPO4OH. The single-ion anisotropy D and the interchain exchange J' in (enH2)0.5VPO4OH and NH4VPO4OH were estimated in density functional calculations to find them very weak compared to the intrachain exchange J.

Quantum critical transition amplifies magnetoelastic coupling in Mn[N(CN)2]2.

We report the discovery of a magnetic quantum critical transition in Mn[N(CN)(2)](2) that drives the system from a canted antiferromagnetic state to the fully polarized state with amplified magnetoelastic coupling as an intrinsic part of the process. The local lattice distortions, revealed through systematic phonon frequency shifts, suggest a combined MnN(6) octahedra distortion+counterrotation mechanism that reduces antiferromagnetic interactions and acts to accommodate the field-induced state. These findings deepen our understanding of magnetoelastic coupling near a magnetic quantum critical point and away from the static limit.

A combination of organic and inorganic cations in the synthesis of transition metal nitrates: preparation and characterization of canted rectangular Ising antiferromagnet (PyH)CsCo2(NO3)6.

Pyridinium cesium cobalt nitrate, (PyH)CsCo2(NO3)6, obtained from a nitric acid solution crystallizes in the orthorhombic space group Pnma with unit cell parameters a = 8.6905(14) Å, b = 11.9599(18) Å, c = 18.386(3) Å, V = 1911.0(5) Å3, and Z = 4. It consists of [Co(NO3)3]- layers, in which each Co2+ ion is connected with four monodentate bridging NO3-groups and one bidentate terminal NO3-group, forming a corrugated rectangular net. Magnetization and specific heat measurements show that (PyH)CsCo2(NO3)6 undergoes a long-range canted antiferromagnetic ordering in two steps at TC1 = 5.0 K and TC2 = 2.6 K. The temperature dependence of the magnetic susceptibility and the field dependence of the magnetization measured for (PyH)CsCo2(NO3)6 show that it is an Ising antiferromagnet. In support of these observations, our DFT + U + SOC calculations show that the Co2+ ions of (PyH)CsCo2(NO3)6 have an easy-axis magnetic anisotropy with preferred spin orientation along the b-axis. To a first approximation, the spin lattice of (PyH)CsCo2(NO3)6 is a weakly alternating Ising antiferromagnetic chain (J1/J2 ∼ 0.85), and these chains interact weakly (J3/J2 ∼ 0.07) to form a rectangular Ising antiferromagnetic lattice. In agreement with the prediction for a rectangular Ising antiferromagnet by Onsager, (PyH)CsCo2(NO3)6 undergoes a long-range antiferromagnetic ordering.

A cascade of magnetic phase transitions and a 1/3-magnetization plateau in selenite-selenate Co3(SeO3)(SeO4)(OH)2 with kagomé-like Co2+ ion layer arrangements: the importance of identifying a correct spin lattice.

We prepared a new compound, Co3(SeO3)(SeO4)(OH)2, having layers in a kagomé-like arrangement of Co2+ (spin S = 3/2) ions. This phase crystallizes in the orthorhombic space group Pnma (62) with unit cell parameters a = 11.225(9) Å, b = 6.466(7) Å and c = 11.530(20) Å. Its layers, parallel to the ab-plane, are made up of Co1O5 square pyramids and Co2O6 and Co3O6 octahedra. As the temperature is lowered, Co3(SeO3)(SeO4)(OH)2 undergoes three successive magnetic transitions at 27.5, 19.4 and 8.1 K, and the magnetization of Co3(SeO3)(SeO4)(OH)2 measured at 2.4 K exhibits a 1/3-magnetization plateau between 7.8 and 19.9 T. The H-T magnetic phase diagram constructed for Co3(SeO3)(SeO4)(OH)2 from ac and dc magnetic susceptibility, specific heat and magnetization measurements contains three magnetic phases I, II and III. Phase I is antiferromagnetic, while phases II and III are ferrimagnetic and responsible for the 1/3-magnetization plateau. To interpret these complex magnetic properties, we identified the correct spin lattice for Co3(SeO3)(SeO4)(OH)2 by evaluating its intralayer and interlayer spin exchanges based on spin-polarized DFT+U calculations.

Giant ferroelectric polarization of CaMn7O12 induced by a combined effect of Dzyaloshinskii-Moriya interaction and exchange striction.

By extending our general spin-current model to noncentrosymmetric spin dimers and performing density functional calculations, we investigate the causes for the helical magnetic order and the origin of the giant ferroelectric polarization of CaMn7O12. The giant ferroelectric polarization is proposed to be caused by the symmetric exchange striction due to the canting of the Mn4+ spin arising from its strong Dzyaloshinskii-Moriya interaction. Our study suggests that CaMn7O12 may exhibit a novel magnetoelectric coupling mechanism in which the magnitude of the polarization is governed by the exchange striction, but the direction of the polarization by the chirality of the helical magnetic order.

Strong Dzyaloshinskii-Moriya interaction and origin of ferroelectricity in Cu2OSeO3.

By performing density functional calculations, we investigate the origin of the Skyrmion state and ferroelectricity in Cu2OSeO3. We find that the Dzyaloshinskii-Moriya interactions between the two different kinds of Cu ions are extremely strong and induce the helical ground state and the Skyrmion state in the absence and presence of a magnetic field, respectively. On the basis of the general model for the spin-order induced polarization, we propose that the ferroelectric polarization of Cu2OSeO3 in the collinear ferrimagnetic state arises from an unusual mechanism, i.e., the single-spin-site contribution due to the spin-orbit coupling.

Observation of a 1/3 magnetization plateau in Pb2Cu10O4(SeO3)4Cl7 arising from (Cu2+)7 clusters of corner-sharing (Cu2+)4 tetrahedra.

A mixed-valence compound Pb2Cu10O4(SeO3)4Cl7 has a complex structure consisting of one nonmagnetic Cu+ (S = 0) ion and four nonequivalent magnetic Cu2+ (S = 1/2) ions. It exhibits antiferromagnetic ordering at TN = 10.2 K. At a temperature below TN, a sequence of spin-flop transition at Bspin-flop = 1.3 T and 1/3 plateau formation at Bspin-flip = 4.4 K is observed in the magnetization curve M(B). The 1/3 magnetization plateau persists at least up to 53.5 T. The spin exchanges of Pb2Cu10O4(SeO3)4Cl7 evaluated by performing energy-mapping analysis based on DFT+U calculations show that the magnetic properties of Pb2Cu10O4(SeO3)4Cl7 are described by the (Cu2+)7 cluster of corner-sharing (Cu2+)4 tetrahedra, and that each (Cu2+)7 cluster has a S = 3/2 spin arrangement in the ground state. The 1/3 magnetization plateau observed for Pb2Cu10O4(SeO3)4Cl7 is explained by the field-induced flip of every second (Cu2+)7 cluster within a unit cell.

General theory for the ferroelectric polarization induced by spin-spiral order.

The ferroelectric polarization of triangular-lattice antiferromagnets induced by helical spin-spiral order is not explained by any existing model of magnetic-order-driven ferroelectricity. We resolve this problem by developing a general theory for the ferroelectric polarization induced by spin-spiral order and then by evaluating the coefficients needed to specify the general theory on the basis of density functional calculations. Our theory correctly describes the ferroelectricity of triangular-lattice antiferromagnets driven by helical spin-spiral order and incorporates known models of magnetic-order-driven ferroelectricity as special cases.

Pressure-induced local structure distortions in Cu(pyz)F2(H2O)2.

We employed infrared spectroscopy along with complementary lattice dynamics and spin density calculations to investigate pressure-driven local structure distortions in the copper coordination polymer Cu(pyz)F(2)(H(2)O)(2). Here, pyz is pyrazine. Our study reveals rich and fully reversible local lattice distortions that buckle the pyrazine ring, disrupt the bc-plane O-H···F hydrogen-bonding network, and reinforce magnetic property switching. The resiliency of the soft organic ring is a major factor in the stability of this material. Interestingly, the collective character of the lattice vibrations masks direct information on the Cu-N and Cu-O linkages through the series of pressure-induced Jahn-Teller axis switching transitions, although Cu-F bond softening is clearly identified above 3 GPa. These findings illustrate the importance of combined bulk and local probe techniques for microscopic structure determination in complex materials.

Ferromagnetically coupled Shastry-Sutherland quantum spin singlets in (CuCl)LaNb2O7.

A thorough crystal structure determination at very low temperature of (CuCl)LaNb2O7, originally proposed as a spin-1/2 square-lattice antiferromagnet, is reported thanks to the use of single-crystal x-ray diffraction and powder neutron diffraction. State-of-the-art calculations (maximum entropy method) reveal that (CuCl)LaNb2O7 is orthorhombic with Pbam symmetry. First-principles calculations demonstrate that the dominant magnetic interactions are antiferromagnetic between fourth nearest neighbors with a Cu-Cl-Cl-Cu exchange path, which lead to the formation of spin singlets. The two strongest interactions between the singlets are ferromagnetic, which makes (CuCl)LaNb2O7 the first system of ferromagnetically coupled Shastry-Sutherland quantum spin singlets.

Magnetoelastic coupling through the antiferromagnet-to-ferromagnet transition of quasi-two-dimensional [Cu(HF2)(pyz)2]BF4 using infrared spectroscopy.

We investigated magnetoelastic coupling through the field-driven transition to the fully polarized magnetic state in quasi-two-dimensional [Cu(HF2)(pyz)2]BF4 by magnetoinfrared spectroscopy. This transition modifies out-of-plane ring distortion and bending vibrational modes of the pyrazine ligand. The extent of these distortions increases with the field, systematically tracking the low-temperature magnetization. These distortions weaken the antiferromagnetic spin exchange, a finding that provides important insight into magnetic transitions in other copper halides.

Hole density dependence of the critical temperature and coupling constant in the cuprate superconductors.

A bond valence sum (BVS) analysis was performed for the p-type cuprate superconductors. The superconducting critical temperature T(c) versus in-plane Cu-O BVS correlation for copper is grouped into classes and subclasses. Only within a class or subclass for which the nonelectronic effect is constant does the variation of the in-plane Cu-O BVS reflect the corresponding change in the hole density n(H) of the CuO(2) layers. This study strongly suggests that the T(c) for every class or subclass of the superconductors is an inverted parabolic function of n(H), and so is the coupling constant lambda for Cooper pair formation.

Hidden fermi surface nesting and charge density wave instability in low-dimensional metals.

The concept of hidden Fermi surface nesting was introduced to explain the general observation that certain low-dimensional metals with several partially filled bands exhibit charge density wave (CDW) instabilities, although their individual Fermi surfaces do not reveal the observed nesting vectors. This concept was explored by considering the Fermi surfaces of the purple bronze AMo(6)O(17) (A = sodium or potassium) and then observing the CDW spatial fluctuations expected from its hidden nesting on the basis of diffuse x-ray scattering experiments. The concept of hidden Fermi surface nesting is essential for understanding the electronic instabilities of low-dimensional metals.

Organic superconductors--new benchmarks.

Recent advances in the design and synthesis of organic synthetic metals have yielded materials that have the highest superconducting transition temperatures (T(c) approximately 13 kelvin) reported for these systems. These materials have crystal structures consisting of alternating layers of organic donor molecules and inorganic anions. Organic superconductors have various electronic and magnetic properties and crystal structures that are similar to those of the inorganic copper oxide superconductors (which have high T(c) values); these similarities include highly anisotropic conductivities, critical fields, and short coherence lengths. The largest number of organic superconductors, including those with the highest T(c) values, are charge-transfer salts derived from the electron donor molecule BEDT-TTF or ET [bis(ethylenedithio)-tetrathiafulvalene]. The synthesis and crystal structures of these salts are discussed; their electrical, magnetic, and band electronic structure properties and their many similarities to the copper oxide superconductors are treated as well.

Color properties and structural phase transition in penta- and hexacoordinate isothiocyanato Ni(II) compounds.

We investigated the optical properties of (NBu(4))(3)[Ni(NCS)(5)], a pentacoordinate Ni compound, and compared the results with the more traditional hexacoordinate analogue (NEt(4))(4)[Ni(NCS)(6)]. On the basis of our complementary electronic structure calculations, the color properties of this high spin complex can be understood in terms of excitations between strongly hybridized orbitals with significant Ni d and ligand character. Variable temperature vibrational studies show mode softening with decreasing temperature and splitting near 200 K, trends that we attribute to improved low temperature intermolecular interactions and a weak structural phase transition, respectively.

Investigation of the scanning tunneling microscopy image, the stacking pattern, and the bias-voltage-dependent structural instability of 1,10'-phenanthroline molecules adsorbed on Au(111) in terms of electronic structure calculations.

A self-assembled monolayer of 1,10'-phenanthroline (phen) molecules on Au(111) was found to undergo a structural phase transition when the bias voltage is switched in scanning tunneling microscopy (STM) experiments (Phys. Rev. Lett. 1995, 75, 2376; Surf. Sci. 1997, 389, 19). The nature of two bright spots representing each phen molecule in the high-resolution STM images of phen molecules on Au(111) was identified by calculating the partial density plots for a monolayer of phen molecules adsorbed on Au(111) with tight-binding electronic structure calculations. The stacking pattern of chains of phen molecules on Au(111) was explained by studying the intermolecular interactions between phen molecules on the basis of first-principles electronic structure calculations for a phen dimer, (phen)(2). The structural instability of phen molecule arrangement caused by the bias-voltage switch was probed by estimating the adsorbate-surface interaction energy with the point-charge approximation for Au(111).

Analysis of Bonding and d-Electron Count in the Transition-Metal Carbides and Transition-Metal-Silicide Carbides with Discrete Linear M-C-M Units (M = Cr, Fe, Re) by Electronic Structure Calculations.

Electronic structures of the silicide carbides Tm(2)Fe(2)Si(2)C, Th(2)Re(2)Si(2)C, and ThFe(2)SiC and the carbide Ho(2)Cr(2)C(3) were calculated, using the extended Hückel tight binding method, to probe the d-electron counts of their transition metal atoms M (Cr, Fe, Re) the bonding of their linear M-C-M (M = Cr, Fe, Re) units. The nature of the short interlayer X.X (X = C, Si) bonds in Tm(2)Fe(2)Si(2)C, Th(2)Re(2)Si(2)C, and Ho(2)Cr(2)C(3) was also examined. Our study shows that the M-C bonds of the M-C-M units exist as double bonds. There is significant bonding in the interlayer Si.Si contacts of the silicide carbides R(2)M(2)Si(2)C (M = Fe, Re). The transition-metal atoms exist as d(10) ions in Tm(2)Fe(2)Si(2)C and Th(2)Re(2)Si(2)C. The d-electron count is slightly lower than d(10) in ThFe(2)SiC and close to d(5) in Ho(2)Cr(2)C(3).

Spin-Spin Interactions in the Oxides A(3)M'MO(6) (M = Rh, Ir; A = Ca, Sr; M' = Alkaline Earth, Zn, Cd, Na) of the K(4)CdCl(6) Structure Type Examined by Electronic Structure Calculations.

The oxides A(3)M'MO(6) (M = Rh, Ir; A = Ca, Sr; M' = alkaline earth, Zn, Cd) of the K(4)CdCl(6) structure type consist of isolated (MO(6))(8)(-) octahedral anions and exhibit an antiferromagnetic ordering at low temperatures. The spin-spin interactions in these oxides, Ca(3)NaMO(6) (M = Ir, Ru), and Sr(3)NaRuO(6) were examined by calculating how strongly the t(2g)-block levels of adjacent (MO(6))((6+)(n)()())(-) (n = 1, 2) anions interact in the presence and absence of the intervening cations A(2+) and M' (n)()(+) (n = 1, 2). Our calculations show that the spin-spin interactions in these oxides are three-dimensional, and the superexchange interactions occur mainly through the short intrachain and interchain M-O.O-M linkages. When the M(n)()(+) cation is very small compared with the A(2+) cation, the intrachain interaction is substantially stronger than the interchain interaction. The opposite is found when the sizes of the M(n)()(+) and A(2+) cations become similar.

Electronic Band Structure and Madelung Potential Study of the Nickelates La(2)NiO(4), La(3)Ni(2)O(7), and La(4)Ni(3)O(10).

Tight-binding electronic band structures and Madelung potentials were calculated for La(2)NiO(4), La(3)Ni(2)O(7), and La(4)Ni(3)O(10) to examine why a metal-to-metal transition occurs in the nickelate Ln(4)Ni(3)O(10) (Ln = La, Nd, Pr). La(4)Ni(3)O(10) and La(3)Ni(2)O(7) are each found to have two hidden one-dimensional (1D) Fermi surfaces, which suggests that both compounds should possess a charge density wave instability. Factors leading to hidden 1D Fermi surfaces in the e(g) block bands of the nickelates were discussed.

Pressure-Induced Changes in the Structure and Band Gap of CsGeX(3) (X = Cl, Br) Studied by Electronic Band Structure Calculations.

Tight-binding electronic band structures of cesium trihalometalates CsGeX(3) (X = Cl, Br) were calculated to examine the pressure-dependence of their crystal structures and band gaps as well as their primitive cubic to rhombohedral structural phase transitions. In agreement with experiment, our calculations show that an increase in the applied pressure decreases the band gap and the stability of CsGeX(3), and the band gap is larger for CsGeCl(3) than for CsGeBr(3). CsGeCl(3) has a much stronger second-order Jahn-Teller instability than does CsGeBr(3) and therefore can adopt a disordered cubic phase unlike CsGeBr(3).